CN1276946C - Flame retardant thermoplastic resin composition - Google Patents
Flame retardant thermoplastic resin composition Download PDFInfo
- Publication number
- CN1276946C CN1276946C CNB018233422A CN01823342A CN1276946C CN 1276946 C CN1276946 C CN 1276946C CN B018233422 A CNB018233422 A CN B018233422A CN 01823342 A CN01823342 A CN 01823342A CN 1276946 C CN1276946 C CN 1276946C
- Authority
- CN
- China
- Prior art keywords
- aryl
- alkyl
- compound
- resin
- thermoplastic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a flame retardant thermoplastic resin composition that contains a phenol resin derivative having good char formability, regardless of the base resin. A flame retardant thermoplastic resin composition according to the present invention comprises (A) 100 parts by weight of a thermoplastic resin as a base resin, (B) about 0.1 SIMILAR 100 parts by weight of a phenol resin derivative, and (C) about 0.1 SIMILAR 50 parts by weight of a phosphorous compound or a mixture of phosphorous compounds.
Description
Technical field
The present invention relates to a kind of thermoplastic resin composition with good flame-retardance.The invention particularly relates to a kind of flame resistance thermoplastic resin compositions that contains formaldehyde-phenol resin derivative.No matter what base resin is, described urea formaldehyde derivative all has good carbon formability.
Background technology
The flame retardant resistance that improves the thermoplastic resin composition for a long time is the major objective of resin R and D.Existing known best method is to prepare flame resistance thermoplastic resin compositions with halogen compounds, at United States Patent (USP) 4,983, discloses with the thermoplastic resin composition of halogen compounds as fire retardant in 658 and 4,883,835.No matter what base resin is, shown good flame with the thermoplastic resin composition of halogen compounds., its shortcoming is this halogen contained compound because the hydrogen halide that himself discharges in the molding process has caused the corrosion of mould itself and just in case this poisonous gas of presence of fire can cause fatal harm.Therefore, not halogen-containing in the art fire retardant has become main perpetual object.
Now, typically not halogen-containing fire retardant is a phosphorus type flame retardant.Phosphorus compound is more superior than halogen compounds aspect the corrosion of mould and toxic gas are discharged.But the flame retardant resistance of phosphorus compound is strong unlike halogen contained compound, and if with a large amount of phosphorus compounds to strengthen flame retardant resistance, thermotolerance will descend.In addition, when using phosphorus compound as fire retardant, will be restricted to the selection of base resin.
The another kind of method that strengthens thermoplastic resin composition's flame retardant resistance is that the material that will have good carbon formability joins in the base resin of carbon formability difference, when burning to form carbon film.This carbon film hinders oxygen, heat and other can quicken resin burnt fuel transfer of gas.
Have the resol of good carbon formability, become the goal in research of flame resistance thermoplastic resin compositions., there is shortcoming in resol, the undercapacity of carbon film, because the polarity of resin, the consistency of resol and other resins is poor, and because the problem of color change takes place in weathering resistance missionary society.
Therefore, the present inventor has developed a kind of flame resistance thermoplastic resin compositions that uses formaldehyde-phenol resin derivative, and it can overcome the shortcoming of resol above-mentioned.In the made flame resistance thermoplastic resin compositions of the present invention, formaldehyde-phenol resin derivative has solved the problem owing to the color change that uses resol to cause, and has increased the consistency with other fluoropolymer resins.This formaldehyde-phenol resin derivative makes flame resistance thermoplastic resin compositions have good carbon formability.
Summary of the invention
An object of the present invention is to provide a kind of no matter what base resin is, all have the thermoplastic resin composition of excellent flame retardancy.
Another object of the present invention provides a kind ofly to be had fine antiultraviolet weathering resistance and with other fluoropolymer resins the thermoplastic resin composition of fine consistency is arranged.
Thereby a further object of the present invention provides a kind of thermoplastic resin composition that hydrogen halide causes the mould corrosion and can not discharge toxic gas when the contingency presence of fire that can not discharge in molding process.
Other purposes of the present invention and advantage will embody in disclosed content and claims subsequently.
The made flame resistance thermoplastic resin compositions of the present invention comprises that (A) 100 parts by weight of thermoplastic resin are as base resin, (B) formaldehyde-phenol resin derivative of about 0.1～100 weight part and (C) phosphorus compound of about 1～50 weight part or the mixture of phosphorus compound.
Embodiment
(A) thermoplastic resin (base resin)
Thermoplastic resin all can be used as base resin arbitrarily in the present invention.When using phosphorus compound as fire retardant material usually, will be restricted to base resin, because be difficult to obtain enough flame retardant effects., in the present invention,, do not have the thermoplastic resin that it is poor that carbon formability or carbon can be shaped row can be used as base resin yet, and enough flame retardant resistances are arranged owing to both used formaldehyde-phenol resin derivative to use poly (phenylene ether) resin yet.
Example as the thermoplastic resin of base resin comprises polyacrylonitrile-butadiene-styrene copolymer (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylic ester copolymer (ASA resin), methacrylate butadi ene styrene copolymer (MBS resin), vinyl cyanide-ethyl propenoate-styrol copolymer (AES resin), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl acrylate (PMMA), polyamide (PA), their multipolymer and alloy in addition.
(B) formaldehyde-phenol resin derivative
When resol was used for the thermoplastic resin composition with the enhancing flame retardant resistance, the shortcoming of resol was the undercapacity of carbon film, because the consistency of the polarity resol of resin and other resins is poor, because the problem of color change takes place in weathering resistance missionary society.The derivative of use resol will overcome the shortcoming of resol.To such an extent as to the use of the derivative of resol makes base resin have good carbon formability to improve flame retardant resistance.The structure of formaldehyde-phenol resin derivative is represented by following molecular formula (I).
R wherein
1Be C
1-34Alkyl; Aryl; Alkyl substituted aryl; Contain O-, N-, the alkyl of P-or S-; Contain O-, N-, the aryl of P-or S-; Contain O-, N-, the alkyl substituted aryl of P-or S-; R
2, R
3, R
4Be hydrogen, C
1-34Alkyl; Aryl; Alkyl substituted aryl; Contain O-, N-, the alkyl of P-or S-; Contain O-, N-, the aryl of P-or S-; Contain O-, N-, the alkyl substituted aryl of P-or S-; And n is from 1 to 10,000 integer, considers mechanical property and processing characteristics, preferred 1 to 300.
During burning, the outflow of combustion gases and the inflow of oxygen and air have been stoped owing to having formed carbon film as the formaldehyde-phenol resin derivative of flame-retardant additive.Formaldehyde-phenol resin derivative has overcome the shortcoming when resol is used for the thermoplastic resin composition.The shortcoming of resol is the undercapacity of carbon film since the polarity of resol it is poor with the consistency of other resins, owing to the problem of weathering resistance difference generation color change.
The preferred embodiment of formaldehyde-phenol resin derivative comprises ortho-cresol novolak Resins, epoxy and phenol epoxy resin.These formaldehyde-phenol resin derivatives are used alone or as a mixture.
With base resin is 100 parts, and the used weight part of formaldehyde-phenol resin derivative is about 0.01 to 100 part.
(C) phosphorus compound
Phosphorus compound used among the present invention comprises phosphate compound, and phosphamide compound contains the positive phosphine compound of oxygen, carboxyl phosphinic compounds, phosphoric acid ester morpholide compound and phosphazene compound.These phosphorus compounds are used alone or as a mixture.Its consumption is the phosphorus compound that adds about 1 to 50 weight part in the base resin of 100 weight parts.These phosphorus compounds have a detailed description below:
Phosphate compound and phosphamide compound: phosphate compound and phosphamide compound are represented by following molecular formula (II):
R wherein
3, R
4And R
5Be hydrogen or C
1-4Alkyl, X are the C that is derived by glycol
6-20Aryl or alkyl substituted C
6-20Aryl.Wherein glycol can be a diphenol, chinol, bisphenol-A and bis-phenol-S.Y is oxygen or nitrogen, and m is 0 to 4.
If m is 0 in the molecular formula (II), compound may be a triphenylphosphate so, Tritolyl Phosphate, Tritolyl Phosphate, tricresyl phosphate (2, the 6-xylyl) ester, tricresyl phosphate (2,4, the 6-trimethylphenyl) ester, tricresyl phosphate (2,4-two trimethylphenylmethane bases) ester, phosphoric acid (2,6-two trimethylphenylmethane bases) three esters and its analogue.If m is 1, compound may be Resorcinol two (biphenyl) phosphoric acid ester, Resorcinol two (2, the 6-xylyl) phosphoric acid ester, Resorcinol two (2,4-two trimethylphenylmethane bases) phosphoric acid ester, chinol (2, the 6-xylyl) phosphoric acid ester, chinol (2,4-two trimethylphenylmethane bases) phosphoric acid ester and its analogue.These phosphorus compounds are used alone or as a mixture.
Contain the positive phosphine compound of oxygen: contain the positive phosphine compound of oxygen and represent by following chemical formula (III):
R wherein
1Be hydrogen, C
1-6Alkyl or C
6-15Aryl, R
2And R
3Be hydrogen or C
1-6Alkyl, and n is 1 to 3.
The preferred embodiment that contains the positive phosphine compound of oxygen is a 2-methyl-2,5-diketo-1-oxa--2-phosphorane and 2-phenyl-2,5-diketo-1-oxa--2-phosphorane.These contain the positive phosphine compound of oxygen and are used alone or as a mixture.
The carboxyl phosphinic compounds: the carboxyl phosphinic compounds is represented by following chemical formula (IV):
R wherein
1Be hydrogen, C
1-12Alkyl, C
6-10Aryl or C
7-15Alkyl substituted aryl, R
2Be C
1-12Alkylidene group, C
1-12Annular alkylidene group, C
6-12Aryl, or C
6-12Alkyl substituted aryl.
The preferred embodiment that contains the positive phosphine compound of oxygen is 2-carboxyl-ethyl-methyl-phospanic acid, 2-carboxyl-ethyl-phenyl-phospanic acid and 2-carboxyl-methyl-phenyl-phospanic acid.These contain the positive phosphine compound of oxygen and are used alone or as a mixture.
Phosphoric acid ester morpholide compound: phosphoric acid ester morpholide compound is represented by following chemical formula V:
R wherein
1Be C
6-20Aryl group or alkyl substituted C
6-20Aryl group, R
2Be C
6-30Aryl group or alkyl substituted C
6-30Aryl group, x are 1 or 2, and n and m are mean polymerisation degree, and n+m is 0 to 5.
In chemical formula V, R
1Be preferably phenyl group or alkyl substituted phenyl group, alkyl wherein is a methyl, ethyl, sec.-propyl, the tertiary butyl, isobutyl-, isopentyl or uncle's pentyl, preferable methyl, ethyl, sec.-propyl or the tertiary butyl.R
2Preferred C
6-30Aryl group or the alkyl substituted C that derives and by Resorcinol, quinhydrones or bisphenol-A
6-30Aryl group.
These phosphoric acid ester morpholide compounds are used alone or as a mixture.
Phosphazene compound: linear phosphazene compound is by following chemical formula (VI) expression, and annular phosphazene compound is represented by following chemical formula (VII).
R wherein
1, R
2, R
3Be alkyl independently, aryl, alkyl substituted aryl, aralkyl, alkoxyl group, aryloxy, amino or hydroxyl.K is from 0 to 10 integer.Wherein alkoxy grp and aryloxy group can be by alkyl, aryl, and amino, hydroxyl, nitrile, nitro has the aryl of hydroxyl and other analogues to replace.
Thermoplastic resin composition of the present invention can add other additives.Additive comprises impact modifier, thermo-stabilizer, and antioxidant, photostabilizer and mineral filler be talcum for example, silicon-dioxide, mica, glass fibre, organic or inorganic pigment and/or dyestuff.Based on the base resin of 100 weight parts, the add-on of additive is 50 weight parts at the most.
Can understand the present invention better by the reference the following examples.The following examples are for the present invention is described, to the present invention without any qualification.Limitation of the invention is in claim subsequently.In the following embodiments, except special stipulation, all umbers and percentage composition all are the weight numbers.
Embodiment
The composition of preparation flame resistance thermoplastic resin compositions is as follows in embodiment 1～12 and comparative example 1～6:
(A) thermoplastic resin (base resin)
(A1) impact resistant polystyrene (HIPS)
Used impact resistant polystyrene is prepared by traditional technology, contains the rubber of 9% weight, and the mean sizes of rubber grain is 1.5 μ m, and molecular-weight average is 220,000.
(A2) SAN graft copolymer
With 50 parts divinyl rubber milk powder, 36 parts of polystyrene, 14 part of third rare nitrile and 150 deionized waters mix.In said mixture, add 1.0 parts of potassium oleates, 0.4 part of cumene hydroperoxide, 0.2 part of chain-transfer agent that contains mercaptan, 0.4 part glucose, the ferrous oxyhydroxide of 0.01 part ferrous acid (iron sulfatehydroxide) and 0.3 part of tetra-sodium sodium salt.Mix 5 hours down to obtain ABS latex at 75 ℃.In this ABS latex, add 0.4 part of sulfuric acid, then coagulation, dry to obtain the Powdered resin (g-ABS) that contains phenylethene grafted copolymer.
(A3) san copolymer
With 75 parts of vinylbenzene, 25 parts of vinyl cyanide, 120 parts of deionized waters, 0.15 part of Diisopropyl azodicarboxylate (AIBN) mixes.In above-mentioned mixing solutions, add 0.4 part of tricalcium phosphate and 0.2 part of chain-transfer agent that contains mercaptan.With above-mentioned solution with being heated to 80 ℃ and be incubated 180 minutes in 90 minutes.With the washing of gained material, dehydration, drying.Thereby obtained styrene-acrylonitrile copolymer (SAN).
(A4) polycarbonate resin
It is 25,000 linear bisphenol A polycarbonate that use has molecular-weight average.
(B) formaldehyde-phenol resin derivative
(B1) use the formaldehyde-phenol resin derivative produced by Korea S Kukdo chemical company (product is by name: YDCN-500-7P), represented by following chemical formula (VIII):
Wherein the mean value of n is 2.3.
(B2) softening temperature is 85 ℃ phenolic novolac 50 gram, and benzyl chloride 200 grams and 150 Virahols that restrain are dissolved in together in 20 milliliters the water and with gained solution and are heated to 70 ℃.With the time that surpasses 1 hour, under agitation the NaOH with 100 grams 20% joins in the above-mentioned solution.After reaction is more than 2 hours, this solution cool to room temperature.Organic layer is separated with water layer, and with distilled water with its washing for several times.With the organic layer vacuum distilling of separating, to remove benzyl chloride and solvent.Gains are dry in baking oven, thus final product obtained, and final product is represented by following molecular formula (IX):
Wherein the mean value of n is 3.4.
(B3) in order to compare with formaldehyde-phenol resin derivative, the use molecular weight is about 1000 novolak phenol aldehyde resin, and it is represented by following molecular formula (X):
Wherein the mean value of n is 5.2.
(C) phosphorus compound
(C1) the use fusing point is 48 ℃ a triphenylphosphine (TPP).
(C2) use at room temperature Resorcinol bisphosphate (RDP) as viscous liquid.
(C3) use the triphenyl morpholide Resorcinol bisphosphate of representing by following chemical formula (XI) (TPP)
Embodiment 1-12
Among embodiment 1-5 and the comparative example 1-3, the composition of composition is shown in the table 1.Resin combination is extruded into ball with the traditional double screw extrusion press under 200～280 ℃.
These resin balls 80 ℃ dry 3 hours down, and with 6 ounces of injection molding machines under 220 ℃～280 ℃, be molded as the sample that is used for measuring limit oxygen index (LDI).Under ASTM D2863 condition, the determination limit oxygen index.
Comparative example 1-6
In the comparative example 1,3 and 5, both without formaldehyde-phenol resin derivative also without resol, in comparative example 2,4 and 6, replace formaldehyde-phenol resin derivative with resol (B3).
Table 1
| Composition | LOI | ||||||||||
| A | B | C | |||||||||
| A1 | A2 | A3 | A4 | B1 | B2 | B3 | C1 | C2 | C3 | ||
| Embodiment 1 | 100 | - | - | - | 10 | - | - | 15 | - | - | 36 |
| 2 | 100 | - | - | - | 10 | - | - | - | 15 | - | 36 |
| 3 | 100 | - | - | - | 10 | - | - | - | - | 15 | 35 |
| 4 | 100 | - | - | - | - | 10 | - | 15 | - | - | 36 |
| 5 | 100 | - | - | - | - | 10 | - | - | 15 | - | 34 |
| 6 | 100 | - | - | - | - | 10 | - | - | - | 15 | 36 |
| 7 | - | 70 | 30 | - | 10 | - | - | 15 | - | - | 35 |
| 8 | - | 70 | 30 | - | - | 10 | - | 15 | - | - | 34 |
| 9 | - | 70 | 30 | - | 10 | - | - | - | 15 | - | 34 |
| 10 | - | 42 | 18 | 40 | 10 | - | - | 15 | - | - | 39 |
| 11 | - | 42 | 18 | 40 | - | 10 | - | 15 | - | - | 36 |
| 12 | - | 42 | 18 | 40 | - | 10 | - | - | - | 15 | 37 |
| Comparative example 1 | 100 | - | - | - | - | - | - | 15 | - | - | 21 |
| 2 | 100 | - | - | - | - | - | 10 | 15 | - | - | 27 |
| 3 | - | 70 | 30 | - | - | - | - | 15 | - | - | 23 |
| 4 | - | 70 | 30 | - | - | - | 10 | 15 | - | - | 29 |
| 5 | - | 42 | 18 | 40 | - | - | - | 15 | - | - | 26 |
| 6 | - | 42 | 18 | 40 | - | - | 10 | 15 | - | - | 30 |
Table 1 demonstrates the LOI of the resin combination of embodiment 1-12 and comparative example 1-6.LOI is high more, just needs many more oxygen resin that burns, and promptly high flame retardant is good more more for LOI.
In embodiment 1-12, use formaldehyde-phenol resin derivative (B1) or (B2).In comparative example 1,3 and 5, neither use formaldehyde-phenol resin derivative also without resol, in comparative example 2,4 and 6, use resol (B3) to replace formaldehyde-phenol resin derivative.The LOI of embodiment 1-12 demonstrates reasonable flame retardant resistance than the height of comparative example 1-6.
Therefore, no matter what base resin is, uses the good formaldehyde-phenol resin derivative of carbon formability, thermoplastic resin composition all to have good flame retardant resistance in the thermoplastic resin composition.Even base resin does not have or the carbon formability is poor, the flame retardant resistance that resol also can provide.
Those of ordinary skills can easily implement the present invention.The scope of the present invention that limits in claims of the present invention, some changes and variation can be predicted.
Claims (5)
1, a kind of flame resistance thermoplastic resin compositions comprises:
(A) 100 parts by weight of thermoplastic resin are as base resin, described base resin is selected from polyacrylonitrile-butadiene-styrene copolymer (ABS resin), the polystyrene resin of modified rubber (HIPS), acrylonitrile-styrene-acrylic ester copolymer (ASA resin), methacrylate butadi ene styrene copolymer (MBS resin), vinyl cyanide-ethyl propenoate-styrol copolymer (AES resin), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polymethylmethacrylate (PMMA), polyamide (PA) and its alloy;
(B) formaldehyde-phenol resin derivative by following chemical formulation of 0.1～100 weight part;
R wherein
1Be C
1-34Alkyl; Aryl; Alkyl substituted aryl; Contain O-, N-, the alkyl of P-or S-; Contain O-, N-, the aryl of P-or S-; Or contain O-, N-, the alkyl substituted aryl of P-or S-; R
2, R
3, and R
4Be hydrogen, C
1-34Alkyl, aryl, alkyl substituted aryl; Contain O-, N-, the alkyl of P-or S-; Contain O-, N-, the aryl of P-or S-; Or contain O-, N-, the alkyl substituted aryl of P-or S-; And n is 1 to 10,000 integer; And
(C) phosphorus compound of 1～50 weight part is as halogen-free flame retardants;
Wherein said phosphorus compound is selected from phosphate compound, phosphamide compound, oxaphosphorane compound, carboxyl phosphinic compounds, phosphoric acid ester morpholide compound, phosphazene compound and its mixture;
Wherein said phosphate compound and phosphamide compound are by following chemical formulation:
R wherein
3, R
4And R
5Be hydrogen or C
1-4Alkyl, X is C
6-20Aryl or the alkyl substituted C that derives and by glycol
6-20Aryl, wherein glycol be between the benzene xylenol, chinol, bisphenol-A and bis-phenol-S, Y are oxygen or nitrogen, and the scope of m is 0 to 4;
Wherein said oxaphosphorane compound is by following chemical formulation:
R wherein
1Be hydrogen, C
1-6Alkyl, or C
6-15Aryl, R
2And R
3Be hydrogen or C
1-6Alkyl, and the scope of n is 1 to 3;
Wherein said carboxyl phosphinic compounds is by following chemical formulation:
R wherein
1Be hydrogen, C
1-12Alkyl, C
6-10Aryl, or C
7-15Alkyl substituted aryl, R
2Be C
1-12Alkylidene group, C
1-12Cyclic alkylidene, C
6-12Aryl or C
6-12Alkyl substituted aryl;
Wherein said phosphoric acid ester morpholide compound is by following chemical formulation:
R wherein
1Be C
6-20Aryl group or alkyl substituted C
6-20Aryl group, R
2Be C
6-30Aryl group or alkyl substituted C
6-30Aryl group, x are 1 or 2, and n and m are number-average degree of polymerizations, and n+m is 0 to 5;
Wherein said phosphazene compound is represented by following chemical formula (VI) or (VII):
R wherein
1, R
2And R
3Be alkyl independently, aryl, alkyl substituted aryl, aralkyl, alkoxyl group, aryloxy, amino or hydroxyl, and k is 0 to 10 integer; Described alkoxyl group and aryloxy group can be by alkyl, aryl, and amino, hydroxyl, nitrile, nitro, or the aryl that has a hydroxyl replaces.
2, the flame resistance thermoplastic resin compositions of claim 1, wherein said formaldehyde-phenol resin derivative are selected from neighbour-cresols novolak Resins, epoxy, phenol epoxy ester and its mixture.
3, the flame resistance thermoplastic resin compositions of claim 1 can also comprise being selected from following additive: anti-impact modifier, thermo-stabilizer, antioxidant, photostabilizer, mineral filler, organic or inorganic pigment and/or dyestuff, the amount of additive is 50 parts at the most in the base resin of per 100 weight parts.
4, the flame resistance thermoplastic resin compositions of claim 3, wherein said mineral filler comprises talcum, silicon-dioxide, mica or glass fibre.
5, the moulded product for preparing by flame resistance thermoplastic resin compositions any among the claim 1-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2001-0031959A KR100406593B1 (en) | 2001-06-08 | 2001-06-08 | Flame Retardant Thermoplastic Resin Composition |
| KR2001/31959 | 2001-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1516721A CN1516721A (en) | 2004-07-28 |
| CN1276946C true CN1276946C (en) | 2006-09-27 |
Family
ID=19710541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018233422A Expired - Fee Related CN1276946C (en) | 2001-06-08 | 2001-12-26 | Flame retardant thermoplastic resin composition |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US7148275B2 (en) |
| EP (1) | EP1404760B1 (en) |
| JP (1) | JP4048168B2 (en) |
| KR (1) | KR100406593B1 (en) |
| CN (1) | CN1276946C (en) |
| AT (1) | ATE387474T1 (en) |
| DE (1) | DE60133047T2 (en) |
| ES (1) | ES2302716T3 (en) |
| WO (1) | WO2002100947A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9602814B2 (en) | 2010-01-22 | 2017-03-21 | Thomson Licensing | Methods and apparatus for sampling-based super resolution video encoding and decoding |
Families Citing this family (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI239342B (en) * | 2000-08-08 | 2005-09-11 | Toray Industries | Flame-retarded resin composition and shaped article made from thereof |
| KR100406593B1 (en) * | 2001-06-08 | 2003-11-20 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| US7138445B2 (en) * | 2000-10-31 | 2006-11-21 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| KR100427531B1 (en) * | 2001-09-13 | 2004-04-30 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| AU2003230910A1 (en) * | 2003-02-06 | 2004-09-06 | Dow Global Technologies Inc. | Halogen free ignition resistant thermoplastic resin compositions |
| KR100552999B1 (en) * | 2003-08-04 | 2006-02-15 | 제일모직주식회사 | Flameproof Thermoplastic Resin Composition |
| EP1756216A4 (en) * | 2004-06-17 | 2010-09-22 | Cheil Ind Inc | Flameproof thermoplastic resin composition |
| KR100650910B1 (en) * | 2004-10-13 | 2006-11-27 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| US7358287B2 (en) * | 2005-05-31 | 2008-04-15 | Ovation Polymer Technology And Engineered Materials, Inc. | Flame retardant polycarbonate composition |
| KR100662184B1 (en) * | 2005-07-22 | 2006-12-27 | 제일모직주식회사 | Halogen-free flameproof thermoplastic resin composition |
| KR100680481B1 (en) | 2005-10-05 | 2007-02-08 | 제일모직주식회사 | Flame retardant high impact polystyrene with good heat resistance and high impact strength |
| KR100787750B1 (en) * | 2005-12-19 | 2007-12-24 | 제일모직주식회사 | Flameproof Thermoplastic Resin Composition |
| KR100654525B1 (en) | 2005-12-30 | 2006-12-05 | 제일모직주식회사 | Salt of carboxyethyl phosphinate ester and flame retardant thermoplastic resin composition containing therof |
| EP1976929A4 (en) * | 2005-12-30 | 2012-07-18 | Cheil Ind Inc | Flame retardant polycarbonate thermoplastic resin composition having good extrusion moldability and impact resistance |
| KR100885819B1 (en) * | 2007-12-18 | 2009-02-26 | 제일모직주식회사 | Branched acrylic copolymer with high refractive index and preparation method thereof |
| KR101004040B1 (en) * | 2007-12-18 | 2010-12-31 | 제일모직주식회사 | Scratch-Resistant Flameproof Thermoplastic Resin Composition with improved compatibility |
| KR100877295B1 (en) | 2007-12-26 | 2009-01-07 | 제일모직주식회사 | Scratch-resistant flameproof thermoplastic resin composition |
| KR100902352B1 (en) * | 2008-03-13 | 2009-06-12 | 제일모직주식회사 | Thermoplastic resin composition with improved compatibility |
| KR100886348B1 (en) * | 2008-04-14 | 2009-03-03 | 제일모직주식회사 | Flame-retardant scratch-resistant thermoplastic resin composition with improved compatibility |
| KR101188349B1 (en) * | 2008-12-17 | 2012-10-05 | 제일모직주식회사 | Polycarbonate resin composition with improved transparency and scratch-resistance |
| KR101066929B1 (en) * | 2008-12-29 | 2011-09-22 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition Having Good Scratch Resistance |
| US8735490B2 (en) * | 2009-12-30 | 2014-05-27 | Cheil Industries Inc. | Thermoplastic resin composition having improved impact strength and melt flow properties |
| KR101425256B1 (en) * | 2011-04-01 | 2014-08-14 | 주식회사 엘지화학 | Thermoplastic abs resin compositions having excellent resistance to flame property |
| CN105504639A (en) * | 2013-07-30 | 2016-04-20 | 江苏理工学院 | Preparation method of halogen-free flame-retardant high impact polystyrene |
| EP2881408B1 (en) | 2013-12-04 | 2017-09-20 | Lotte Advanced Materials Co., Ltd. | Styrene-based copolymer and thermoplastic resin composition including the same |
| CN103804757A (en) * | 2014-01-20 | 2014-05-21 | 苏州新区华士达工程塑胶有限公司 | Flame-retardant ultraviolet-proof polyethylene plastic |
| US9902850B2 (en) | 2014-06-26 | 2018-02-27 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition |
| US9856371B2 (en) | 2014-06-27 | 2018-01-02 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and low-gloss molded article made therefrom |
| US9850333B2 (en) | 2014-06-27 | 2017-12-26 | Lotte Advanced Materials Co., Ltd. | Copolymers and thermoplastic resin composition including the same |
| US9790362B2 (en) | 2014-06-27 | 2017-10-17 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded article made using the same |
| CN104045956A (en) * | 2014-07-16 | 2014-09-17 | 苏州新区华士达工程塑胶有限公司 | Improved AES |
| CN104299687B (en) * | 2014-10-11 | 2016-07-27 | 国家电网公司 | A kind of fire-proof insulation cable |
| KR101822697B1 (en) | 2014-11-18 | 2018-01-30 | 롯데첨단소재(주) | Thermoplastic resin composition with excellent appearance and molded article using thereof |
| CN105482353A (en) * | 2015-12-22 | 2016-04-13 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Wear resistant resin material composition for printer and preparation method as well as application of wear resistant resin |
| TW201811909A (en) * | 2016-05-19 | 2018-04-01 | 可樂麗股份有限公司 | Methacrylic resin composition and shaped product |
| CN105860394A (en) * | 2016-06-02 | 2016-08-17 | 陈昌 | Synthetic-fiber-added environment-friendly material and preparation method thereof |
| CN106221103A (en) * | 2016-08-05 | 2016-12-14 | 苏州创佳塑胶有限公司 | High shiny black high glaze exempts from the material and preparation method thereof that sprays paint |
| CN108623972A (en) * | 2018-05-25 | 2018-10-09 | 安徽尼古拉电子科技有限公司 | A kind of impact-resisting wear-resisting cable jacket material and preparation method thereof |
| CN110256802A (en) * | 2019-06-10 | 2019-09-20 | 安徽蓝润自动化仪表有限公司 | A kind of potent heat-proof combustion-resistant plastics power control cabinet case material and preparation method thereof |
| CN112552634A (en) * | 2020-11-30 | 2021-03-26 | 金发科技股份有限公司 | Flame-retardant ABS composition and preparation method and application thereof |
| CN115612273B (en) * | 2022-11-30 | 2023-03-10 | 苏州优利金新材料有限公司 | Preparation method of polycarbonate with high thermal stability |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS536016B2 (en) * | 1974-10-17 | 1978-03-03 | ||
| CA1121535A (en) * | 1978-10-05 | 1982-04-06 | William R. Haaf | Flame retardant phosphorus/nitrogen additives for thermoplastics |
| DE3401835A1 (en) * | 1984-01-20 | 1985-07-25 | Basf Ag, 6700 Ludwigshafen | HALOGEN-FREE, FLAME-RETARDED THERMOPLASTIC MOLDING |
| EP0174493B1 (en) * | 1984-08-17 | 1988-05-25 | Bayer Ag | Thermoplastic moulding masses with flame-retarding properties |
| US4883835A (en) * | 1987-04-17 | 1989-11-28 | Bayer Aktiengesellschaft | Flame resistant antistatic polycarbonate moulding compounds |
| JP2681659B2 (en) * | 1988-07-19 | 1997-11-26 | 日本合成化学工業株式会社 | Laminated structure |
| US5218030A (en) * | 1989-02-08 | 1993-06-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Curable polyphenylene ether resin composition and a cured resin composition obtainable therefrom |
| FR2659969A1 (en) * | 1990-03-26 | 1991-09-27 | Norsolor Sa | FLAME RETARDANT POLYMER COMPOSITIONS, PROCESS FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF FLAME RETARDANT INDUSTRIAL ARTICLES |
| KR0149450B1 (en) * | 1992-12-29 | 1998-10-15 | 구창남 | Inflammable resin composition |
| JPH0776649A (en) | 1993-07-14 | 1995-03-20 | Denki Kagaku Kogyo Kk | Flame-retardant resin composition |
| EP0661342B1 (en) * | 1993-12-28 | 2003-04-02 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Additive for thermoplastic resins and flame retardant resin composition |
| EP0712899B1 (en) * | 1994-11-19 | 1999-06-02 | General Electric Company | Hydrolytic stable glass fiber reinforced polyester resins |
| JPH08208884A (en) * | 1995-01-30 | 1996-08-13 | Denki Kagaku Kogyo Kk | Flame-retardant resin composition |
| DE69629971T2 (en) | 1995-02-27 | 2004-07-22 | Mitsubishi Chemical Corp. | Hammematic thermoplastic resin composition |
| WO1997012925A1 (en) * | 1995-09-29 | 1997-04-10 | Toshiba Chemical Corporation | Halogen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
| JPH10273520A (en) * | 1997-03-31 | 1998-10-13 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition |
| JP2000143930A (en) * | 1998-11-16 | 2000-05-26 | Toray Ind Inc | Flame-retarded thermoplastic resin composition and molded product comprising the same |
| JP2000239525A (en) * | 1999-02-16 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition and layer insulation adhesive |
| JP2001002685A (en) * | 1999-06-21 | 2001-01-09 | Chemiprokasei Kaisha Ltd | Phosphazene composition and its production |
| KR100540582B1 (en) * | 1999-07-12 | 2006-01-10 | 제일모직주식회사 | Flame retardant thermoplastic resin composition |
| KR100401326B1 (en) * | 2001-06-08 | 2003-10-10 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| KR100372569B1 (en) * | 2000-10-31 | 2003-02-19 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| KR100406593B1 (en) * | 2001-06-08 | 2003-11-20 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| US7138445B2 (en) * | 2000-10-31 | 2006-11-21 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
-
2001
- 2001-06-08 KR KR10-2001-0031959A patent/KR100406593B1/en not_active IP Right Cessation
- 2001-12-26 JP JP2003503708A patent/JP4048168B2/en not_active Expired - Fee Related
- 2001-12-26 WO PCT/KR2001/002262 patent/WO2002100947A1/en active IP Right Grant
- 2001-12-26 AT AT01274303T patent/ATE387474T1/en not_active IP Right Cessation
- 2001-12-26 DE DE60133047T patent/DE60133047T2/en not_active Expired - Lifetime
- 2001-12-26 US US10/480,056 patent/US7148275B2/en not_active Expired - Lifetime
- 2001-12-26 EP EP01274303A patent/EP1404760B1/en not_active Expired - Lifetime
- 2001-12-26 CN CNB018233422A patent/CN1276946C/en not_active Expired - Fee Related
- 2001-12-26 ES ES01274303T patent/ES2302716T3/en not_active Expired - Lifetime
-
2006
- 2006-11-16 US US11/600,155 patent/US7439287B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9602814B2 (en) | 2010-01-22 | 2017-03-21 | Thomson Licensing | Methods and apparatus for sampling-based super resolution video encoding and decoding |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020094307A (en) | 2002-12-18 |
| ES2302716T3 (en) | 2008-08-01 |
| US20040192814A1 (en) | 2004-09-30 |
| WO2002100947A1 (en) | 2002-12-19 |
| DE60133047D1 (en) | 2008-04-10 |
| ATE387474T1 (en) | 2008-03-15 |
| EP1404760B1 (en) | 2008-02-27 |
| KR100406593B1 (en) | 2003-11-20 |
| CN1516721A (en) | 2004-07-28 |
| JP4048168B2 (en) | 2008-02-13 |
| US20070060679A1 (en) | 2007-03-15 |
| EP1404760A4 (en) | 2005-05-04 |
| DE60133047T2 (en) | 2009-03-12 |
| JP2004529258A (en) | 2004-09-24 |
| US7439287B2 (en) | 2008-10-21 |
| EP1404760A1 (en) | 2004-04-07 |
| US7148275B2 (en) | 2006-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1276946C (en) | Flame retardant thermoplastic resin composition | |
| CN1276945C (en) | Flame retardant thermoplastic resin composition | |
| KR100810111B1 (en) | Flameproof thermoplastic resin composition | |
| CN1281681C (en) | Flame retardant thermoplastic resin composition | |
| TWI439506B (en) | Impact resistant, flame retardant thermoplastic molding composition | |
| KR100400964B1 (en) | Oligomeric Phosphorus Acid Ester Morpholide Compound and Flame Retardant Thermoplastic Resin Compsition Containing Thereof | |
| US20070155874A1 (en) | Flameretardant thermoplastic resin composition | |
| JP2010523734A (en) | Flameproof copolymer and flame retardant thermoplastic resin composition using the same | |
| CN101061179A (en) | Flame retardant thermoplastic resin composition | |
| KR20180063338A (en) | Reinforced thermoplastic resin composition and molded article thereof | |
| CN1835999A (en) | Flameproof thermoplastic resin composition | |
| CN1832997A (en) | Flameproof thermoplastic resin composition | |
| KR20190081630A (en) | Thermoplastic resin composition and article produced therefrom | |
| KR101304151B1 (en) | Polycarbonate Moulding Materials with Improved Hydrolytic Resistance | |
| KR20190081868A (en) | Thermoplastic resin composition and article produced therefrom | |
| KR101296850B1 (en) | Flame retardant resin composition having improved heat stability, and molded artice manufactured therefrom | |
| WO2009066830A1 (en) | Non-halogen flameproof polycarbonate resin composition | |
| KR100986016B1 (en) | Polycarbonate molding compounds | |
| CN1266206C (en) | Styrenic thermoplastic resin composition | |
| CN1433448A (en) | Flame-retardant resin composition and molded artide obtained therefrom | |
| CN1832996A (en) | Flameproof thermoplastic resin composition | |
| JP2004018734A (en) | Flame-retardant resin composition and molding prepared therefrom | |
| KR100508855B1 (en) | Flameproof Thermoplastic Resin Composition | |
| JPH07238218A (en) | Flame-retardant resin composition | |
| JP2004018733A (en) | Flame-retardant resin composition and molding prepared therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170224 Address after: Jeonnam, South Korea Patentee after: LOTTE ADVANCED MATERIALS Co.,Ltd. Address before: Gyeonggi Do, South Korea Patentee before: Samsung SDI Co.,Ltd. Effective date of registration: 20170224 Address after: Gyeonggi Do, South Korea Patentee after: Samsung SDI Co.,Ltd. Address before: Gyeongbuk, South Korea Patentee before: Cheil Industries Inc. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060927 Termination date: 20201226 |